CN109616632B - Manganese-based solid solution material, preparation method thereof, positive electrode and battery - Google Patents

Manganese-based solid solution material, preparation method thereof, positive electrode and battery Download PDF

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CN109616632B
CN109616632B CN201811446822.7A CN201811446822A CN109616632B CN 109616632 B CN109616632 B CN 109616632B CN 201811446822 A CN201811446822 A CN 201811446822A CN 109616632 B CN109616632 B CN 109616632B
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manganese
solid solution
based solid
lithium
solution material
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檀满林
付晓宇
张亮
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Shenzhen Research Institute Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract

A preparation method of a manganese-based solid solution material comprises the following steps: providing a lithium source and a manganese source, and dissolving the lithium source and the manganese source in a solvent to form a solution; putting the solution into a closed container for heating reaction, wherein the solution generates a precipitate after the heating reaction; filtering, washing and drying the precipitate; and placing the dried precipitate into a container, heating and preserving heat, and naturally cooling to room temperature to obtain the manganese-based solid solution material. The general formula of the manganese-based solid solution material is LiMnxOySaid LiMnxOyIs Li2MnO3And LiMn2O4A solid solution of (2). The invention also provides a positive electrode and a battery.

Description

Manganese-based solid solution material, preparation method thereof, positive electrode and battery
Technical Field
The invention relates to the field of energy storage, in particular to a preparation method and application of a battery material.
Background
At present, as one of the energy storage modes with excellent performance, the lithium ion battery has a wider and wider application range, which requires that the lithium ion battery has better performance in the aspects of energy density, cycling stability, rate performance and the like, and has the advantages of low preparation cost, good safety performance, environmental friendliness and the like. The lithium battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode comprises a matrix, a positive electrode material coated on the matrix and a conductive material, wherein the positive electrode material is a key material of the lithium battery, and the lithium-rich manganese-based positive electrode material is favored by researchers with higher specific capacity, but has higher first irreversible capacity and poor rate capability, and the defects in the performance hinder the development and application of the material.
Disclosure of Invention
In view of the above, it is necessary to provide a method for preparing a manganese-based solid solution material to solve the above problems.
In addition, the manganese-based solid solution material prepared by the preparation method of the manganese-based solid solution material is also provided.
A preparation method of a manganese-based solid solution material comprises the following steps:
s1, providing a lithium source and a manganese source, and dissolving the lithium source and the manganese source in a solvent to form a solution;
s2, putting the solution into a closed container for heating reaction, wherein the solution generates a precipitate after the heating reaction;
s3, filtering, washing and drying the precipitate;
and S4, placing the dried precipitate into a container, heating and preserving heat, and naturally cooling to room temperature to obtain the manganese-based solid solution material.
Further, in step S1, adding an additive, wherein the additive includes one or more of benzoic acid, urea, and oxalic acid.
Further, in step S2, the heating temperature is 160 ℃ to 200 ℃ and the heating time is 10h to 30 h.
Further, in step S4, the heating and heat preservation temperature is 400-800 ℃, and the heating and heat preservation time is 6-10 h.
Furthermore, the molar ratio of the lithium ions provided by the lithium source to the manganese ions provided by the manganese source is 2.7-3.7.
Further, the lithium source is one or more of lithium sulfate, lithium nitrate, lithium acetate, lithium chloride, lithium oxalate and lithium hydroxide metal inorganic/organic acid salt, and the manganese source is one or more of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride metal inorganic/organic acid salt.
The general formula of the manganese-based solid solution material is LiMnxOySaid LiMnxOyIs Li2MnO3And LiMn2O4Wherein x is more than or equal to 0.5 and less than or equal to 4, and x is 0.33-0.5.
Furthermore, x is more than or equal to 0.5 and less than or equal to 0.8, and the ratio of x to y is 0.35-0.40.
A positive electrode comprising the manganese-based solid solution material.
A battery comprising the positive electrode.
The manganese-based solid solution material prepared by the preparation method of the manganese-based solid solution material provided by the invention is used as a battery anode material, and has higher and more stable charge-discharge specific capacity and longer cycling stability; and the particle size of the manganese-based solid solution material and the element ratio of Li, Mn and O can be controlled by different preparation parameters (such as the molar ratio of lithium ions to manganese ions, the solvothermal reaction time and temperature, the crystallization reaction time and temperature and the like), so that the LiMn of the manganese-based solid solution material can be changedxOyMiddle Li2MnO3And LiMn2O4The charge-discharge specific capacity and the cycle life of the button cell can be correspondingly controlled.
Drawings
FIG. 1 is a flow chart of the preparation of a manganese-based solid solution material according to an embodiment of the present invention.
FIG. 2A is a Scanning Electron Microscope (SEM) image of a comparative material prepared in a comparative example, and FIG. 2B is an SEM image of a manganese-based solid solution material prepared in example 1 of the present invention.
FIG. 3 is an X-ray diffraction (XRD) pattern of manganese-based solid solution materials prepared according to example 1 of the present invention and comparative example.
FIG. 4 shows the current density of 125mA g for the button cell of the present invention in example 1 and comparative example-1Cycle performance test chart below.
Fig. 5 is a graph showing the rate performance test of the button cell of the embodiment 1 and the comparative example.
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Referring to fig. 1, the present invention provides a method for preparing a manganese-based solid solution material, comprising the steps of:
s1, providing a lithium source and a manganese source, wherein the lithium source and the manganese source are dissolved in a solvent according to a certain proportion to form a solution;
s2, putting the solution into a closed container for heating reaction, wherein the solution generates a precipitate after the heating reaction;
s3, filtering, washing and drying the precipitate;
and S4, placing the dried precipitate into a container for heating and heat preservation, crystallizing the dried precipitate at a higher temperature to form a solid solution, and naturally cooling to room temperature to obtain the manganese-based solid solution material.
In step S1, the solvent may be ethanol or deionized water, the lithium source and the manganese source at least include two groups, the groups include a solvophilic group and a solvophobic group, and the metal ions in the lithium source and the manganese source belong to the solvophobic group.
In step S1, the lithium source is one or more of inorganic/organic acid salts of metals such as lithium sulfate, lithium nitrate, lithium acetate, lithium chloride, lithium oxalate, and lithium hydroxide, the manganese source is one or more of inorganic/organic acid salts of metals such as manganese sulfate, manganese nitrate, manganese acetate, and manganese chloride, a molar ratio of lithium ions provided by the lithium source to manganese ions provided by the manganese source is 2.7-3.7, and an amount of the lithium ions to the manganese ions is to compensate for a loss of lithium elements in a subsequent heating process.
In step S1, a step of adding an additive capable of decomposing to generate a large amount of gas when heated is further included, and the metal ions enter the bubbles randomly, so that the addition of the additive facilitates uniform mixing of the lithium ions and the manganese ions and reduction of the particle size of the product.
In step S2, the heating reaction is a solvothermal reaction, the solvothermal reaction temperature is 160 ℃ to 200 ℃, the solvothermal reaction time is 10h to 30h, the temperature is maintained for a period of time, during the solvothermal reaction process, a large amount of gas generated by the additive drives the lithium ions and the manganese ions to move and diffuse at high speed, so that the lithium ions and the manganese ions are uniformly mixed, and after the solvothermal reaction is completed, Li is formed2CO3And MnCO3The additive includes, but is not limited to, CO3 2-and-COOH, -CO, such as urea, benzoic acid, oxalic acid, etc.
In step S3, the precipitate generated after the reaction is taken out, and then is washed with clean water or ethanol to obtain a pure precipitate, and then is dried to obtain a dried precipitate.
In step S4, the method further includes a step of grinding the obtained dried precipitate to obtain fine and uniform powder, and then heating and maintaining the ground precipitate in a heating device at 400-800 ℃ for 6-10 hours, wherein the heating is performed at the temperature at which the precipitate reacts and crystallizes to form a solid solution, so as to obtain the manganese-based solid solution material.
The invention also provides a manganese-based solid solution material prepared by the preparation method, and the general formula of the manganese-based solid solution material is LiMnxOySaid LiMnxOyIs Li2MnO3And LiMn2O4Wherein x is more than or equal to 0.5 and less than or equal to 4, and x is 0.33-0.5.
Furthermore, x is more than or equal to 0.5 and less than or equal to 0.8, and the ratio of x to y is 0.35-0.40.
Further, the Li2MnO3Is layered, the LiMn2O4Is of spinel crystal form, said Li2MnO3And LiMn2O4Interconversion at 400-800 ℃ to form LiMnxOySolid solution.
Further, the LiMnxOyLiMn in (C)2O4The valence state of the Mn element is +3 or +4, the position of partial Mn element is occupied by Li element, the valence state of partial Mn element is increased, and LiMn element is occupied by Li element2O4The spinel structure can still provide a three-dimensional channel for the transmission of lithium ions; in addition, LiMn due to spinel structure2O4Mn during charging and discharging3+Disproportionation occurs to cause distortion of spinel structure, thereby affecting the LiMnxOyThe stability of the electrochemical performance when the material is used as an electrode material and the increase of the valence state of the Mn element are beneficial to improving the stability of the electrochemical performance and playing a role in reducing capacity attenuation.
The invention also provides a positive electrode, which comprises a current collector and a coating material arranged on the surface of the current collector, wherein the coating material comprises the manganese-based solid solution material, a conductive material and a binder, the manganese-based solid solution material, the conductive material and the binder are dispersed in a solvent according to a certain proportion, and are uniformly mixed to obtain a dispersion solution, and then the dispersion solution is coated on the current collector and is dried and sliced to obtain the positive electrode.
The present invention also provides a lithium battery including the positive electrode, the negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte.
The present invention will be specifically described below with reference to examples and comparative examples.
Example 1
Dissolving 0.013mol of lithium acetate and 0.008mol of manganese acetate in 80mL of ethanol solvent, namely the molar ratio of lithium ions to manganese ions is 3.25, then adding 0.035mol of urea serving as an additive, and stirring for 2 hours to form a uniform solution; putting the solution into a 100mL reaction kettle for solvothermal reaction, preserving the temperature at 200 ℃ for 20h, and naturally cooling to room temperature; pouring the reacted product into a centrifuge tube for centrifugation, removing supernatant, leaving precipitate, washing and drying to obtain clean and dry precipitate; and (3) putting the clean and dry precipitate into a tubular furnace for crystallization treatment, heating to 600 ℃ at the speed of 8 ℃/min, preserving the heat for 8h at the temperature of 600 ℃, and then naturally cooling to room temperature to obtain the manganese-based solid solution material.
Example 2
The difference from example 1 is: in the example, the temperature of the solvothermal reaction was 180 ℃ and the time was 10 hours.
The other steps are the same as in example 1 and are not repeated here.
Example 3
The difference from example 1 is: the temperature of the solvothermal reaction in the example was 160 ℃ and the time was 30 h.
The other steps are the same as in example 1 and are not repeated here.
Example 4
The difference from example 1 is: the temperature of the crystallization reaction in this example was 400 ℃ and the time was 10 hours.
The other steps are the same as in example 1 and are not repeated here.
Example 5
The difference from example 1 is: the temperature of the crystallization reaction in this example was 800 ℃ and the time was 6 hours.
The other steps are the same as in example 1 and are not repeated here.
Example 6
The difference from example 1 is: the molar ratio of lithium ions to manganese ions in this example was 3.61.
The other steps are the same as in example 1 and are not repeated here.
Example 7
The difference from example 1 is: in this example, the molar ratio of lithium ions to manganese ions was 2.73.
The other steps are the same as in example 1 and are not repeated here.
Specific treatment conditions of examples 1 to 7 are shown in Table 1.
TABLE 1 EXAMPLES 1 TO 7 concrete treatment conditions
Figure BDA0001885909960000061
Figure BDA0001885909960000071
Comparative example 1
30mL of 1mol/L MnSO are prepared respectively4Solution and 100mL of 3mol/L Na2CO3The solution is ready for use; then adding the MnSO4The solution was poured into a nitrogen-filled reaction kettle and stirred, and the Na was titrated2CO3Adding MnSO into the solution4Generating coprecipitation reaction in the solution, and continuously introducing nitrogen in the titration process; after titration, continuously stirring for 3 hours in a nitrogen atmosphere, stopping stirring, sealing and standing for 12 hours to obtain a precipitate; washing and drying the precipitate to obtain a clean and dry precipitate, wherein the clean and dry precipitate is MnCO3(ii) a Weighing appropriate amount of MnCO3And Li2CO3Said MnCO3And Li2CO3The molar ratio of (1) to (2) is 4:3, then the mixture is fully mixed and placed in a tube furnace for crystallization treatment, the temperature is raised to 600 ℃ at the speed of 8 ℃/min, the temperature is kept at 600 ℃ for 8h, and then the mixture is naturally cooled to room temperature to obtain a comparison material.
Scanning electron microscope tests are carried out on the manganese-based solid solution material prepared in the example 1, the test results are shown in fig. 2A and 2B, fig. 2A and 2B are the test results under the same magnification speed, fig. 2A is the test result of a comparative example, which shows that the particle size of the comparative material prepared in the comparative example is 500-1000 nm, and fig. 2B is the test result of the example 1, which shows that the particle size of the manganese-based solid solution material prepared in the example 1 is less than 100nm, which belongs to a nanoscale material, so that the particle size of the manganese-based solid solution material prepared in the example 1 by adopting the solvothermal method is about one tenth of the particle size of the comparative material prepared in the comparative example by adopting the coprecipitation method, and the particle size of the material is effectively reduced by adopting the solvothermal.
Referring to FIG. 3, the precipitates prepared in example 1 and comparative example were subjected toXRD test shows that the precipitate prepared by the solvothermal method in example 1 and the precipitate prepared by the coprecipitation method in the comparative example have clear diffraction peaks, the positions and the intensities of the diffraction peaks are basically the same, and the same diffraction peaks belong to MnCO3The only difference is that the precipitate prepared in example 1 has one more diffraction peak at the position of 21 degrees, and the more diffraction peak belongs to Li2CO3Indicating that the precipitate prepared in example 1 is MnCO3And Li2CO3Thus demonstrating the solvothermal method of mixing together the lithium and manganese elements of a lithium and manganese source.
The manganese-based solid solution material prepared in example 1 and the comparative material prepared in comparative example were used as the positive electrode material of a lithium battery, and a 2032 type button cell was assembled in a glove box filled with high-purity argon gas, using a lithium sheet as the counter electrode. Testing the button cell by using a Land (blue electricity) cell testing system to perform electrochemical performance test at room temperature, wherein the electrochemical performance test comprises a cycle performance test and a rate performance test, and the current density of the cycle performance test is 125mA g-1And the charge and discharge voltage range is set to be 2-4.8V.
Referring to fig. 4, the button cell assembled with the materials prepared in example 1 and comparative example were tested for cycle performance at a current density of 125mA g-1After 50 times of cycles, the specific discharge capacity of the button cell assembled by the material prepared in the example 1 is maintained at 190mA h g-1While the control group was maintained at 160mA hr g-1And in the whole circulation process, the capacity of the button cell does not fade, which indicates that the stability of the material is better.
Referring to fig. 5, the button cell assembled by the materials prepared in example 1 and comparative example were tested for rate capability, and the current density of the rate capability test was 25, 50, 125, 250, 500, 1250mA g-1The charge-discharge specific capacity rises after 5 times of circulation under each current density under the same current density test, which is caused by the activation process of the electrode material and passes through a large multiplying powerAfter cycling, the specific discharge capacity of the button cell assembled by the material prepared in example 1 reaches 148mA h g-1The manganese-based solid solution material prepared in example 1 can be charged and discharged at a large rate, and still can maintain a high specific charge-discharge capacity.
Further, button cells were prepared from the manganese-based solid solution materials prepared in examples 2 to 7, and electrochemical performance tests were performed, the specific test method was the same as example 1, and the test results of example 1 and the comparative example are shown in table 2.
TABLE 2 electrochemical test results of inventive examples 1-7 and comparative examples
Figure BDA0001885909960000081
Figure BDA0001885909960000091
As can be seen from table 2, compared with the comparative example, the manganese-based solid solution material prepared by the preparation method of the manganese-based solid solution material provided by the invention has higher and more stable charge-discharge specific capacity and longer cycling stability as a battery positive electrode material. Furthermore, the method for preparing the manganese-based solid solution material can control the particle size and the element ratio of Li, Mn and O of the manganese-based solid solution material through different preparation parameters (such as the molar ratio of lithium ions to manganese ions, the solvothermal reaction time and temperature, the crystallization reaction time and temperature and the like), thereby changing the LiMn of the manganese-based solid solution materialxOyMiddle Li2MnO3And LiMn2O4The charge-discharge specific capacity and the cycle life of the button cell can be correspondingly controlled.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.

Claims (8)

1. The preparation method of the manganese-based solid solution material is characterized by comprising the following steps of:
s1, providing a lithium source, a manganese source and an additive, dissolving the lithium source, the manganese source and the additive in a solvent to form a solution, wherein the additive comprises CO3 2-Or a compound of a-COOH group, wherein the lithium source is one or more of lithium sulfate, lithium nitrate, lithium acetate, lithium chloride, lithium oxalate, lithium hydroxide metal inorganic acid salt and metal organic acid salt, and the manganese source is one or more of manganese sulfate, manganese nitrate, manganese acetate, manganese chloride, metal inorganic acid salt and metal organic acid salt;
s2, placing the solution into a closed container for heating reaction, wherein the solution generates a precipitate after the heating reaction, and the heating temperature is 160-200 ℃;
s3, filtering, washing and drying the precipitate;
and S4, placing the dried precipitate into a container for heating and heat preservation, wherein the heating temperature is 400-800 ℃, and then naturally cooling to room temperature to obtain the manganese-based solid solution material.
2. The method of producing a manganese-based solid solution material according to claim 1, wherein said additive comprises one or more of benzoic acid and oxalic acid.
3. The method for producing a manganese-based solid solution material according to claim 2, wherein in step S2, the heating time is 10 to 30 hours.
4. The method for producing a manganese-based solid solution material according to claim 3, wherein in step S4, the heating and holding time is 6 to 10 hours.
5. The method according to claim 1, wherein the molar ratio of lithium ions supplied from the lithium source to manganese ions supplied from the manganese source is 2.7 to 3.7.
6. A manganese-based solid solution material, which is prepared by the method for preparing the manganese-based solid solution material according to any one of claims 1 to 5, wherein the general formula of the manganese-based solid solution material is LiMnxOySaid LiMnxOyIs Li2MnO3And LiMn2O4Wherein x is more than or equal to 0.5 and less than or equal to 0.8, and x is 0.35-0.40.
7. A positive electrode comprising the manganese-based solid solution material according to claim 6.
8. A battery comprising the positive electrode of claim 7.
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